JP2019509381A - Compositions containing organosiloxane nanolatex and preparation of organosiloxane nanolatex - Google Patents

Abstract

(A) Organosiloxane monomer of the general formula M _a ^Mv _{b Dc} D ^v _{d Te} T ^v _f Q _g where M = R ₁ R ₂ R ₃ SiO _1/2 ,
^{_{M v = R 4 R 5 R}} u SiO 1/2,
D = R ₆ R ₇ SiO _2/2 ,
^{_{D v = R 8 R u SiO}} 2/2,
T = R ₉ SiO _3/2 ,
T ^v = R _u SiO _3/2 and Q = SiO _4/2
Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ each independently have hydrogen, a hydroxyl group, up to 100 carbon atoms, A hydrocarbyl group which may contain at least one heteroatom; R _u is a free radical polymerizable group; subscripts a, b, c, d, e, f and g are each independently 0-10 And b + d + f is a condition of at least 1, p, q and r are integers independently selected from 0 to 100, the subscript h is 0 or 1, and ( b) Hydrophobic hybrid organosiloxane nanolatex containing a copolymer of a monomer having a group R _u of the organosiloxane monomer (a) and a free radical copolymerizable group.
[Selection figure] None

Description

This application claims priority of US patent application Ser. No. 15 / 066,395 filed Mar. 10, 2016, the entire contents of which are hereby incorporated by reference in their entirety.
The present invention relates to organosiloxane latex, its preparation and personal care products containing it.

  Various types of organosiloxanes are used in personal care compositions, for example, to impart or enhance one or more aesthetic, sensory and / or functional properties that have become highly desirable by consumers. Often incorporated into skin and hair care products and cosmetics. For example, organosiloxanes have lotions, skin cleansers, body wash, razor moisturizing strips, shaving gels, bar soaps, antiperspirants, deodorants to give the following products a soft and satisfying feel when they are applied: May be included in formulations for skin care products such as sunscreens and lip balms.

  Hair care products such as shampoos, conditioners, hair colours, hair removal agents, etc. can be blended with organosiloxanes to give consumers an impression of quality and luxury.

  Similarly, cosmetic compositions such as foundations, concealers, serums, blushers, mascaras, lipsticks, lip glosses, etc. may contain organosiloxanes to enhance sensory effects as perceived by consumers.

According to the present invention,
(A) Organosiloxane monomer having the general formula M _a ^Mv _{b Dc} D ^v _{d Te} T ^v _f Q _g where M = R ₁ R ₂ R ₃ SiO _1/2 ,
^{_{M v = R 4 R 5 R}} u SiO 1/2,
D = R ₆ R ₇ SiO _2/2 ,
^{_{D v = R 8 R u SiO}} 2/2,
T = R ₉ SiO _3/2 ,
T ^v = R _u SiO _3/2 and Q = SiO _4/2
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ each independently have hydrogen, a hydroxyl group, up to 100 carbon atoms, and at least 1 A hydrocarbyl group that may contain 1 heteroatom; R _u is a free radical polymerizable group; the subscripts a, b, c, d, e, f and g are each independently from 0 to 10,000. a range of one with the proviso that b + d + f>1; and hydrophobic containing (b) a copolymer of a monomer having a group R _u and free-radically copolymerizable group organosiloxane monomer (a) (copolymerizate) Hybrid organosiloxane nanolatex is provided.

  The hydrophobic properties of the organosiloxane nanolatex herein are functional properties that are highly demanded of resistance to water washing, which is the ability of this latex to correspond to long-term wearability, such as personal care products. Things are especially desirable. While not wishing to be bound, it is believed that the improved resistance of the hydrophobic hybrid organosiloxane nanolatex to water washing is due at least to its excellent film forming behavior and / or its greater hydrophobicity.

  In the present specification and claims, the following terms and expressions are to be understood as indicated.

  The singular forms “a”, “an”, and “the” include the plural and reference to a particular numerical value includes at least that particular value, unless the context clearly indicates otherwise.

  All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary terms (eg, “to etc.”) provided herein are merely intended to better illustrate the present invention and are not otherwise claimed. As long as it does not limit the scope of the present invention.

  No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.

  “Comprising”, “including”, “containing”, “characterized by” and their grammatical equivalents do not exclude additional unlisted elements or method steps An inclusive or open-ended term but is understood to include the more restrictive terms “consisting of” and “consisting essentially of”.

  It is understood that any numerical range recited herein includes all subranges within that range and any combination of the various endpoints of such ranges or subranges.

  Any compound, material disclosed explicitly or implicitly in the specification and / or claims as belonging to a structurally, compositionally and / or functionally related compound, substance or group of substances Or substances include individual representatives of the group and all combinations thereof.

  The expression “hydrocarbyl group” includes alkyl, alkenyl, alkynyl, cyclic alkyl, cyclic alkenyl, cyclic alkynyl, aryl, aralkyl and allenyl, any one having one or more hydrogen atoms that may contain heteroatoms removed. Means hydrocarbon.

  The term “alkyl” refers to any monovalent saturated straight, branched or cyclic hydrocarbon group; the term “alkenyl” refers to any one containing one or more carbon-carbon double bonds. Means a monovalent straight chain, branched or cyclic hydrocarbon group, wherein the attachment site of the group can be a carbon-carbon double bond or any other in it; and the term "alkynyl" Means a monovalent straight-chain, branched or cyclic hydrocarbon group containing one or more carbon-carbon triple bonds and optionally one or more carbon-carbon double bonds, wherein the group bonds The moiety is a carbon-carbon triple bond, a carbon-carbon double bond, or other moiety therein. Examples of alkyl include methyl, ethyl, propyl and isobutyl. Examples of alkenyl include vinyl, propenyl, allyl, methallyl, ethylidenyl norbornane, ethylidene norbornyl, ethylidenyl norbornene and ethylidene norbornenyl. Examples of alkynyl include acetylenyl, propargyl and methylacetylenyl.

  The expressions “cyclic alkyl”, “cyclic alkenyl” and “cyclic alkynyl” refer to bicyclic, tricyclic and higher order cyclic structures as well as said cyclic structures further substituted with alkyl, alkenyl and / or alkynyl groups. Including. Representative examples include norbornyl, norbornenyl, ethylnorbornyl, ethylnorbornenyl, cyclohexyl, ethylcyclohexyl, ethylcyclohexenyl, cyclohexylcyclohexyl and cyclododecatrienyl.

  The term “aryl” means any monovalent aromatic hydrocarbon group; the term “aralkyl” refers to the same number and number of the same and / or different aryl groups in which one or more hydrogen atoms are the same (herein Definition) means any alkyl group (as defined herein); the term “allenyl” refers to the same and / or different alkyl groups (wherein one or more hydrogen atoms are the same number). Means any aryl group (as defined herein) substituted with Examples of aryl include phenyl and naphthalenyl. Examples of aralkyl include benzyl and phenethyl. Examples of allenyl include tolyl and xylyl.

  The term “heteroatom” means any group 13-17 element other than carbon and includes, for example, oxygen, nitrogen, silicon, sulfur, phosphorus, fluorine, chlorine, bromine and iodine.

As described above, in the organosiloxane monomer (a), R _{1 to} R ₉ each independently have hydrogen, a hydroxyl group, or up to 100 carbon atoms, and may contain at least one heteroatom. A good hydrocarbyl group.

  In one embodiment, the hydrocarbyl group, when present, comprises up to 60 carbon atoms, in another embodiment up to 30 carbon atoms, and in yet another embodiment up to 20 carbon atoms.

  Useful hydrocarbyl groups are alkyl groups, examples of which are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl and tert-pentyl; such as n-hexyl Hexyl; heptyl such as n-heptyl; n-octyl, isooctyl, octyl such as 2,2,4-trimethylpentyl; nonyl such as n-nonyl; decyl such as n-decyl; and cyclopentyl; Includes cycloalkyl such as cyclohexyl, cycloheptyl and methylcyclohexyl. Examples of alkenyl groups include vinyl, propenyl, allyl, methallyl, cyclohexenyl, norbornenyl, ethyl norbornenyl, ethylidenyl norbornane, ethylidene norbornyl, ethylidenyl norbornene and ethylidene norbornenyl. Examples of the alkynyl group include acetylenyl, propargyl and methylacetylenyl. Examples of aryl groups are phenyl, naphthyl, o-, m- and p-tolyl, xylyl, ethylphenyl and benzyl.

As described above, in the organosiloxane monomer (a), the R _u are free radical polymerizable group. Thus, for example, each R _u can be independently selected from groups such as alkenyl, alkynyl, acrylate, acrylamide, methacrylate, methacrylamide, and the like.

In one embodiment, the free radical polymerizable group R _u of the monomer (a) can be one ethylenically unsaturated group of the following formulas I, II (a), II (b) and II (c):

Wherein each R ₁₀ is independently selected from linear or branched alkyl groups of up to 10 carbon atoms that may contain at least one heteroatom; A ₁ and A ₂ are each as follows: A monomer (b) and a free radical-addable olefinically unsaturated group, and the subscripts p, q and r each independently range from 0 to 100, and the subscript h is 0 or 1 is there.

In one embodiment of formula II (a), II (b) and / or II (c), A ₁ and / or A ₂ are independently a group of formula III:

Wherein R ₁₁ , R ₁₂ and R ₁₃ are independently selected from hydrogen and hydrocarbyl groups of up to 5 carbon atoms, Y is nothing or has 2 to 16 carbon atoms; A linker group selected from divalent aliphatic, alicyclic or aromatic hydrocarbon groups which may contain at least one heteroatom.

  Examples of useful monomers (a) include vinyl functional polysilicones, hydroxy functional polysilicon acrylates, organic modified silicone (meth) acrylates, organic modified silicone (meth) acrylamides and derivatives thereof.

Monomer (b) is any of a monomer having a group R _u and free-radically copolymerizable group organosiloxane monomer (a). In one embodiment, a single monomer (b) is copolymerized with single or multiple monomers (a), and in other embodiments, two or more monomers (b) are combined with single or multiple monomers (a). Copolymerize.

  Examples of useful monomers (b) are acrylic acid, methacrylic acid, their esters and their amide derivatives such as methyl acrylate, butyl acrylate, propyl acrylate, N, N-dimethylacrylamide, N-isopropylacrylamide, 2- Ethylhexyl acrylate, cyclohexyl acrylate, vinyl acrylate, allyl acrylate, hydroxyethyl acrylate, perfluoroethyl acrylate, isobornyl acrylate, lauryl arylate, phenoxyethyl acrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, acrylamide, methacrylamide, acrylic Silane, methacrylic silane, methacryloxyl silane, 2-hydroxyethyl Methacrylate, 3- [tris (trimethylsiloxy) silyl] propyl methacrylate, acrylate and methacrylate functional carbosilane, hexafunctional urethane acrylate, dipentaerythritol pentaacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tri Acrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, butanediol diacrylate, tripropylene glycol diacrylate, trimethylolpropane trimethacrylate, oligofunctional urethane acrylate, tetraacrylate monomer, polyester acrylate oligomer, and their Set Is Align.

The free radical polymerizable monomer (b) can also be selected from ethylenically unsaturated monomers, many of which are butadiene, styrene, ethylstyrene, divinylbenzene, N-vinylpyrrolidone, N-vinyl lactam, vinyl halide. , vinyl acetate, vinyl alcohol, vinyl ethers, allyl alcohol, other capable of reacting with R _u groups of the monomers of allyl polyether and polyorganosiloxane (a) are known in the art.

  Another embodiment in which the weight ratio of total monomer (a) to total monomer (b) can vary widely, and in one embodiment the weight ratio of (a) to (b) is 99.9-0.1. Then, the weight ratio of (a) to (b) is 99 to 1, and in yet another embodiment, the weight ratio of (a) to (b) is 95 to 5. The viscosity of the nanolatex can vary widely, for example, 0.1-250 cps in one embodiment, 0.5-230 cps in another embodiment, and 1-200 cps in yet another embodiment. Similarly, the particle size of the nanolatex can be varied, for example 10-990 nm in one embodiment, 20-800 nm in another embodiment, 25-500 nm in yet another embodiment.

  According to one embodiment of the free radical emulsion copolymerization process capable of preparing the nanolatex of the present invention, the at least one free radical polymerizable monomer (a) is at least one free radical polymerizable monomer (b). Combined with one or more surfactants and one or more auxiliary stabilizers in an aqueous medium and utilized high speed mixing using a rotor-stator mixing system at 5000 to 50,000 rpm, utilizing pressures ranging from 10 to 2000 bar. Emulsification under high shear mixing such as high pressure homogenization, 0.1-16 kW sonication and combinations thereof to produce an emulsion in which the oil phase has a particle size of 10-990 nm. When one or more free radical initiators are added to the emulsion, the copolymerization is from 1 minute to 48 hours, preferably from 5 minutes to 48 minutes, more preferably from 15 minutes to 24 hours, preferably from 1 to 200 ° C. Is carried out under conditions including a temperature of 15 to 150 ° C, more preferably 30 to 100 ° C. Stirring conditions depend on the reaction conditions, the composition of the reaction medium, and the stirring method to provide the hydrophobic hybrid organosiloxane nanolatex herein.

  In one embodiment, the hydrophobic hybrid organosiloxane nanolatex exhibits a measure of its hydrophobicity of at least 50 °, preferably at least 60 °, more preferably at least 70 °, and is itself a sunscreen, waterproof mascara. Represents resistance to water washing, a highly desirable property for many types of personal care products such as eyeliner, lip color and liquid foundation.

  In one embodiment, the surfactant concentration comprises 0.01 to 25 wt%, preferably 0.05 to 20 wt%, more preferably 0.1 to 10 wt%, and the co-stabilizer concentration is 0. 0.01 to 20% by weight, preferably 0.05 to 10% by weight, more preferably 0.1 to 5% by weight.

In another embodiment of the free radical emulsion copolymerization process herein, after copolymerization, a hydrophobic hybrid organosiloxane nanolatex is produced and dried to yield a flexible film with good physical integrity. The mini-emulsion method is used. This process includes the following steps;
Step 1: A homogenous mixture of monomers (a) and (b) and a co-stabilizer (hereinafter referred to as the oil phase) is mixed with 1 to 10% by weight of surfactant or surfactant and co-stabilizer with respect to the oil phase. To form a crude emulsion having a particle size in the range of 0.1 to 990 nanometers;
Step 2: The crude emulsion from Step 1 is subjected to high energy mixing at 1-80 ° C. using, for example, a high pressure homogenizer, microfluidizer or ultrasonic mixing device to produce a particle size in the oil phase range of 10-990 nm. Providing a miniemulsion having improved stability over the crude emulsion of step 1; and Step 3: monomers (a) and (b) in the miniemulsion of step 2 at a temperature of 10-90 ° C. Copolymerization by adding one or more suitable water-soluble and / or oil-soluble free radical initiators.

  The surfactant can be selected from anionic, cationic, zwitterionic and nonionic surfactants and combinations thereof. The co-stabilizer can be selected from compounds with limited water solubility such as, for example, dodecane, cetyl alcohol, cetostearyl alcohol, and combinations thereof.

  In one embodiment, the surfactant is, for example, dodecyl-1 acid sulfate, tetradecyl-1 acid sulfate, octadecyl-1 acid sulfate, dodecane-1-sulfonic acid, tetradecan-1-sulfonic acid, tetradecane-1. -Alkali metal salts of long chain alkyl sulfates and sulfonates such as sulfonic acid, hexadecane-sulfonic acid and octadecane-sulfonic acid, and salts of long chain sulfonated paraffinic hydrocarbons and combinations thereof.

The initiator can be, for example, hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, organic peroxides, azo compounds, and combinations thereof. The initiator may also be composed of coinitiators such as Fe, Cr ²⁺ , V ²⁺ , Ti ³⁺ , Co ²⁺ , Cu ⁺ . An initiator is added to the emulsion where copolymerization of monomers (a) and (b) is initiated. Depending on the nature of the selected initiator, a polymerization temperature of 40-100 ° C. and a reaction time of 1-10 hours are generally suitable.

  Optional ingredients

  The organosiloxane latex composition of the present invention may also include one or more optional ingredients, such as optional ingredients of known and conventional personal care products used in conventional amounts. Among these ingredients, other silicones, surfactants, emulsifiers, solvents such as linear and cyclic siloxanes, organic esters, alkanes such as isododecane, isohexadecane, emollients, moisturizers, humectants, dyes, colorants , Perfumes, antiseptics, antioxidants, biocides, biostats, antiperspirants, release agents, hormones, enzymes, pharmaceuticals, vitamin substances, hydroxy acids, retinal, retinol derivatives, niacinamide, skin lightening agents, salts, Electrolytes, alcohols, polyols, esters, scattering agents and / or absorbers for ultraviolet light, plant extracts, peptides, proteins, organic oils, gums, sugars, oligosaccharides, polysaccharides, derivatives, waxes, film formers, enhancers Adhesives, particulate fillers, plasticizers, wetting agents, occlusive properties, sensory enhancers, resins and optically active particles, etc. It can be mentioned. These compounds can be added before, during or after the polymerization of the organosiloxane.

  Use of personal care

  The hydrophobic hybrid organosiloxane nanolatex herein can improve the wear resistance and sensory characteristics of a wide range of personal care products, including deodorants, antiperspirants, antiperspirants / deodorants, Stick and roll-on products, skin lotion, moisturizer, cosmetic liquid, cleansing product, styling gel, hair dye, hair color product, hair straightener, nail polish, nail polish remover, sunscreen, anti-aging product, lipstick, lip Cream, lip gloss, foundation, face powder, eyeliner, eye shadow, blusher, makeup, serum, mascara, moisturizing preparation, foundation, concealer, body and hand preparation, skin care preparation, Ace and neck preparations, fragrance preparations, soft focus applications, night and daytime skin care preparations, tanning preparations, hand liquids, personal care non-woven applications, baby lotions, facial cleansing products, hair cuticle coats, gels , Foam bath, body wash, scrub cleaner, controlled release personal care product, hair shampoo, hair conditioner, hair spray, skin care moisturizing mist, skin wipe, pore skin wipe, pore cleaner, injury reducing agent, skin remover, skin Drug delivery for topical application of exfoliation promoters, skin taoles and fabrics, hair removal preparations, personal care lubricants, nail coloring preparations, and pharmaceutical compositions applied to the skin It is a system.

  In the following examples, the nanolatex of the present invention is produced by a process that includes high pressure homogenization and emulsion copolymerization. High pressure homogenization results in a more stable latex after copolymerization, ie a miniemulsion that is substantially free of coagulum and thus has improved shelf life, with the oil phase having a narrow nanometer size. Films obtained from the hydrophobic hybrid organosiloxane nanolatexes herein are typically transparent and glossy, which is a highly desirable property for many types of personal care products, which include sun protection. Skin care creams and lotions, moisturizers, anti-aging formulations; BB creams (essentials); hair care products such as hair creams, serums and styling agents; color cosmetics such as lipsticks, nail paints, mascaras, foundations and lotions; and Cleansing products such as soaps, hand wash, shampoos and conditioners.

Comparative Example Preparation of the hydrophilic organosiloxane latex of Example 1 of US Pat. No. 6,207,782.

  The silicone polyether acrylate corresponding to polysiloxane B of US Pat. No. 6,207,782 was slowly added to the following water / surfactant mixture followed by the initiator. Filling was as follows: 40 g silicone polyether acrylate, 156 g water, 4 g sodium lauryl sulfate and 0.2 g potassium persulfate. The emulsion was heated to 75-80 ° C. for 1-2 hours with stirring. After cooling to room temperature, solid sodium bicarbonate was added to adjust the pH of the hydrophilic latex-containing emulsion to neutral.

Examples 1-4
Preparation of monomer (a): Trisiloxane polyether methacrylate Trisiloxane polyether methacrylate (monomer (a)) was prepared in two steps. In the first step, 1.3 mol of allyl polyether of general structure H ₂ C═C (H) CH ₂ O (CH ₂ CH ₂ O) _n H (n = 0, 1, 3 and 8) was used. The hydrosilylation of hexamethyltrisiloxane [(CH ₃ ) ₃ SiO— (H) Si (CH ₃ ) O—Si (CH ₃ ) ₃ ] was carried out at 80 ° C. in the presence of 10 ppm Karstedt catalyst. Each of the resulting silicone polyethers was then placed in an individual three-necked flask and cooled to 0 ° C., after which 1.1 molar equivalents of triethylamine was added. To each flask, an equimolar amount of methacrylic chloride (in relation to hydroxyl groups) dissolved in 20% by weight of dry methyl ethyl ketone (MEK) was added dropwise. When the addition was complete, the reaction mixture was mixed for an additional 3 hours at ambient temperature. The white precipitate of triethylammonium chloride was removed by filtration and the filtrate was subjected to solvent removal at 40 ° C. under a reduced pressure of 10 mbar. The resulting four monomers (a) were subjected to some methacrylic polyether (n = 0 in Example 1, n = 1 in Example 2, n = 3 in Example 3, n = 8 in Example 4) by NMR. It was determined to be a methacrylic silicone polyether containing.

Examples 5-15
Preparation of hydrophobic hybrid organosiloxane nanolatex Formation of miniemulsion An oil phase was prepared by dissolving the co-stabilizer cetyl alcohol in a mixture of butyl acrylate (BA) and methyl methacrylate (MMA). The methacrylated silicone polyethers of Examples 1-4 were individually dissolved in the oil phase. The aqueous phase was prepared with sodium lauryl sulfate (SLS) in water. Both the oil and water phases are mixed with a magnetic stirrer for 10 minutes at 1000 rpm to provide a crude miniemulsion and then sonicated with a GE601 ultrasonic device for 5 minutes, 0.5 second pulse, or CAT X520 Rotar -Stator, homogenized at 22,000 rpm using a 20 mm shaft to provide a miniemulsion. The temperature was maintained at 5 ° C. during sonication / homogenization to prevent or reduce polymerization.

  The composition of the miniemulsion copolymerization reaction mixture (all amounts in grams) is shown in Table 1 below.

B. Copolymerization of miniemulsion to provide minilatex Batch miniemulsion copolymerization was performed in a 250 mL round bottom flask equipped with a reflux condenser, stirrer and nitrogen inlet. Each miniemulsion was added to the flask and kept under a nitrogen atmosphere. When the temperature reached 70 ° C., potassium persulfate as an initiator was placed in the flask. All four copolymerizations were carried out at 70 ° C. Samples were taken at regular intervals while measuring the conversion by gravimetry. The properties of the nanoesters and the films obtained therefrom are shown in Table 2.

Example 16
Preparation of bis (methacrylyl polyether) -functionalized polydimethylsiloxane, Mn ca. 2400 To a round bottom flask equipped with stir bar, reflux condenser and nitrogen inlet was added 200 g of L-8620 (a silicone poly available from Momentive). Ether surfactant) and 123 g of triethylamine were charged and the flask was flushed with nitrogen. The reaction mixture was placed under positive nitrogen pressure and charged with 58 g (15% w / w) of p-toluenesulfonyl chloride in batches of 4 equal portions at 15 minute intervals. After completion of the reaction, excess p-toluenesulfonyl chloride was neutralized with 2.5 g (0.7% w / w) water and 13 g (3.5% w / w) sodium bicarbonate. The reaction mixture was stirred for an additional hour and filtered to give a colorless liquid. The reaction was monitored by ¹ H NMR spectroscopy.

A round bottom flask equipped with a stir bar and reflux condenser was charged with 20 g of bis (p-toluenesulfonyl polyether functionalized polydimethylsiloxane and 20 g of cyclohexane. The reaction mixture was phased with 200 ppm of butylated hydroxyl toluene. 150 mg cetyl tertiary ammonium chloride was added as a transfer catalyst, the reaction mixture was placed under positive nitrogen pressure, 1.7 g sodium methacrylate was added and the reaction mixture was refluxed at 85 ° C. After the copolymerization was complete The reaction mixture was cooled to room temperature and filtered, and the cyclohexane solvent was removed from the filtrate to give a pale yellow liquid, the reaction was monitored by ¹ H NMR spectroscopy.

Example 17
Preparation of bis (methacrylyl) -functionalized polydimethylsiloxane, Mn ca. 3500 In a round bottom flask equipped with stir bar, reflux condenser and addition funnel, 48 g allyl glycidyl ether and 150 g bis (hydrido) terminated polydimethylsiloxane (Mn approx. 3100) was filled. The reaction mixture was heated to 80 ° C. and charged with 5 ppm hexachloroplatinic acid (10% w / w in 2-propanol). After the first exotherm, 350 g of bis (hydrido) terminated polydimethylsiloxane was added at three intervals. An additional 5 ppm of hexachloroplatinic acid was added during the final filling of the hydride. After the final exotherm, the temperature of the reaction mixture was raised to 90-95 ° C. and stirred for 2 hours. After the reaction was completed, excess allyl glycidyl ether was removed under vacuum to give a straw yellow liquid. The reaction was monitored by ¹ H NMR spectroscopy.

In a round bottom flask equipped with a stir bar and reflux condenser, 375 g bis (allylglycidyl ether) functionalized polydimethylsiloxane, as described above, 22 g methacrylic acid (5.4% w / w) and 300 ppm butyl. Hydroxytoluene was added. The reaction mixture was flushed with nitrogen and 1 g of triethylamine (0.25% w / w) was added under positive pressure. The reaction mixture was heated to 95 ° C. and stirred for 16-20 hours. After completion of the reaction, 100 ppm 2,2,6,6-tetramethyl-1-piperidinyloxy was added and the reaction was subjected to vacuum at 95 ° C. and 30 mbar to remove excess methacrylic acid. The reaction mixture was then stirred on Tulsion T-66 MP resin to remove traces of triethylamine. The reaction mixture was then filtered to give a pale yellow viscous liquid. The reaction was monitored by ¹ H NMR spectroscopy.

Example 18
Preparation of bis (methacrylyl) -functionalized polydimethylsiloxane, Mn ca. 2400 In a round bottom flask equipped with stir bar, reflux condenser and addition funnel 78 g 4-vinyl-1-cyclohexene 1,2-epoxide and 500 g bis (Hydride) -terminated polydimethylsiloxane (Mn about 2200) was added. The reaction mixture was heated to 75 ° C. at which time 10 ppm Karstedt catalyst (2% in xylene) was added and the reaction mixture was further heated to 90-95 ° C. A hydride fluid was added dropwise to the mixture to prevent runaway reaction due to exotherm. After completion of the reaction, excess 4-vinyl-1-cyclohexene 1,2-epoxide was removed under vacuum to give a straw yellow liquid. The reaction was monitored by ¹ H NMR spectroscopy.

A round bottom flask equipped with a stir bar and reflux condenser was charged with 500 g of the above bis (4-vinyl-1-cyclohexene 1,2-epoxide) -functionalized polydimethylsiloxane and heated to 75 ° C. At this point, 2000 ppm titanium isopropoxide and 300 ppm butylated hydroxyl toluene were added to the reaction mixture and further heated to 90-95 ° C. 42 g of methacrylic acid was then added dropwise to the reaction mixture and the mixture was stirred until the reaction was complete. The reaction product was cooled to ambient temperature and passed over Tulsion ACR-499 resin to remove traces of methacrylic acid. The product was further filtered to give a pale yellow viscous liquid. The reaction was monitored by ¹ H NMR spectroscopy.

Examples 19-28
Preparation and copolymerization of miniemulsions to provide nanolatex By dissolving the acrylated organosiloxane of Examples 16-18 as monomer (a), butyl acrylate as monomer (b), and cetyl alcohol as a co-stabilizer. Individual oil phases were prepared. Individual aqueous phases were prepared by dissolving 70% sodium lauryl ether sulfate (SLES) in water. While stirring at 500 to 600 rpm, the oil phase was gradually added to the aqueous phase. Each of the resulting coarse emulsions was homogenized using a CAT X520 rotor-stator, 15000 rpm, 30 mm shaft or microfluidizer to obtain a miniemulsion. The temperature was maintained at 15-20 ° C. to prevent or limit the polymerization.

  The components of the miniemulsion are shown in Table 3.

  Copolymerization within each miniemulsion was carried out in a round bottom flask equipped with a reflux condenser and stirrer and fed with a positive stream of nitrogen. Potassium persulfate as an initiator was added to each miniemulsion, which was then heated to 65 ° C. Samples of each reaction mixture were taken at regular intervals and the conversion was determined gravimetrically.

  The data in Table 4 shows that the nanolatex of the present invention in most cases has a lower viscosity than that of Comparative Example 1. Lower viscosity is advantageous for the production of personal care compositions. In addition, the much smaller particle size of all nanolatexes herein improves the stability of the retention period, most of which improves the transparency (lack of haze) of Comparative Example 1. Such properties make the nanolatex of the present invention technically superior to the latex of Comparative Example 1 in cosmetic applications.

Example 29
Preparation of Methacrylated Silicone Emulsion 49.14 parts by weight of dimethiconol having a viscosity of about 0.7 Pa · s at 25 ° C. and 0.86 parts by weight of 3- (methacryloxy) propylmethyldiethoxysilane are mixed together to give 4 50 parts of ethoxylated cetearyl alcohol, 0.5 parts by weight sodium cetearyl sulfate and 6 parts by weight deionized water were added at an increased filling rate and mixing rate to obtain a stable emulsion. Deionized water was added to the emulsion containing oil. The pH was adjusted to 2 and neutralized until the internal viscosity became 6 Pa · s or less.

  35 parts by weight of the emulsion was heated to 80 ° C., 0.05 parts by weight of ammonium persulfate in 10 parts by weight of deionized water, 8.75 parts by weight of methyl methacrylate, 8.75 parts by weight of butyl acrylate, 0 parts of ethoxylated cetearyl alcohol A premix of 5 parts by weight and 5 parts by weight of deionized water was added. The copolymerization reaction was performed for 2 hours. Filled with deionized water and preservatives, a methacrylated silicone emulsion having a copolymer content of 35% by weight was obtained.

Example 30
Preparation of functionalized silicone / lauryl methacrylate emulsion. 49.67 parts by weight of dimethiconol having a viscosity of s and 0.33 parts by weight of 3- (methacryloxy) propylmethyldiethoxysilane were mixed together, 4 parts by weight of PEG-40 stearate, 0.5 parts by weight of A mixture of sodium cetearyl sulfate and 6 parts by weight of deionized water was added at increasing filling and mixing rates to obtain a stable emulsion followed by deionized water and containing 50% oil. It was. The pH was adjusted to 2 and the internal viscosity was 3 Pa.s. Neutralize until s is reached.

  56 parts by weight of the emulsion was heated to 80 ° C., 0.035 parts by weight ammonium persulfate in 10 parts by weight deionized water, 7 parts by weight lauryl methacrylate, 0.5 parts by weight PEG-40 stearate and 4 parts by weight. A portion of a mixture of deionized water was added. The copolymerization reaction was carried out for 3 hours. Filled with deionized water and preservative, a functionalized silicone / LMA emulsion having a copolymer content of 35% by weight was obtained.

  The contact angles of the dried films obtained from the latexes of Comparative Examples 1, 5 and 22 were measured by contact angle goniometry. The contact angle is a measure of the hydrophobicity of the film and indicates the resistance to washing of the film, and thus the washout resistance of the nanolatex from which the film is obtained. A latex polymer film was prepared by stretching a test latex on a glass substrate to provide a 200 μm wet film. The coated substrate was placed in a 45 ° C. oven for 12 hours. The dried coated substrate was then placed on a Ram Hart contact angle goniometer model 250. A 5 μL drop of distilled deionized water was transferred to the surface via a syringe. The water drop was equilibrated for 1 minute and the contact angle was measured via the supplied software. The contact angle was measured as the angle relative to the glass substrate coated with the leading edge of the drop. The greater the angle, the more hydrophobic the film-coated surface. The contact angles were as shown in Table 5 below.

  As the data in Table 5 indicate, the films formed from the latexes of Examples 5 and 22 exhibited much higher contact angles than the film formed from the latex of Comparative Example 1. A higher contact angle, as described above, means greater hydrophobicity corresponding to improved water wash resistance of personal care products formulated with such latexes.

Example 31
Preparation of Functionalized Silicone / Acrylate / Styrene Emulsion 49.14 parts of dimethiconol having a viscosity of about 0.55 Pa · s at 25 ° C. and 0.86 parts of 3- (methacryloxy) propyltrimethoxysilane are mixed together A mixture of 4 parts by weight allyl alcohol, 0.5 parts by weight sodium cetearyl sulfate and 6 parts by weight deionized water is added at an increased fill rate and mixing rate to provide a stable emulsion followed by deionized water. Emulsion containing 50% oil. The pH was adjusted to 2 and the internal viscosity was 6 Pa.s. Neutralize until s is reached.

  Heat 56 parts by weight of the emulsion to 80 ° C., 0.035 parts ammonium persulfate in 5 parts by weight deionized water, 5 parts by weight butyl acrylate, 2 parts by weight styrene, 0.5 parts by weight ethoxylated cetearyl. A mixture containing alcohol and 4 parts by weight of deionized water was added. The copolymerization reaction was carried out for 3 hours. Deionized water and preservatives were added to obtain a functionalized silicone / acrylate / styrene emulsion having a solid content of 48% by weight.

Example 32
Sunscreen compositions were prepared using the amounts (grams) of the ingredients shown in Table 6 below (all amounts expressed in weight percent).

SPF measurements were made on films obtained from the sunscreen composition of Example 32 applied to simulated human skin (Vitro-Skin®, IMS Inc.) using a Labsphere UV analyzer 2000S. A 20 mg / cm ² sunscreen composition was uniformly applied to Vitro-Skin®, followed by a portion of Vitro-Skin® in water for 40 minutes. The SPF measured after drying the Vitro-Skin (R) part latex for 20 minutes was 39.

Example 33
A BB cream composition was prepared in the amounts (grams) shown in Table 7 below using the following ingredients.

  Phase C and Phase D were added to Phase B and heated to 85 ° C. with stirring until a homogeneous mixture was obtained. Phase A was also heated to 85 ° C. and then added to the combined phase B, phase C and phase D. The resulting mixture was stirred at high speed to produce a uniform cream mixture. After the addition of sodium chloride, the cream was homogenized at 11,000 rpm for 2 minutes at 85 ° C. After homogenization, the mixture was cooled to ambient temperature with slow stirring.

Example 34
A mascara composition having the components and amounts shown in Table 8 below was prepared.

  Phase B ingredients were heated to 85 ° C. and mixed until a homogeneous phase was obtained. In a separate container, the water was heated to 85 ° C., after which hydroxyethyl cellulose, black iron oxide and the latex of Example 22 were added with constant stirring to obtain Phase A. Phase B was added to Phase A under high speed [rpm] with stirring at 85 ° C. Mixing was continued until a uniform cream mixture was obtained. The resulting mascara composition was cooled to ambient temperature.

Example 35; Comparative Example 2
Additional mascara compositions were prepared using the amounts (grams) of ingredients shown in Table 9 below.

  Phase A ingredients were mixed by hand and stirred at 500 rpm for 30 minutes at 85 ° C. Thereafter, phase B was added to phase A. Phase C ingredients were mixed together, heated to 85 ° C. to 90 ° C. and added to the combined A and B phases with stirring at 85 ° C. and 500 rpm for 5 minutes. Individual compositions were further mixed for 1 minute at 2,000 rpm.

  The water resistance of the mascara compositions of Example 34 and Comparative Example 2 was tested by applying each composition to in vitro eyelashes (Ardell Runway Lawes). After drying, the eyelashes were immersed in water and shaken by hand for 10 seconds. The mascara composition of Comparative Example 2 did not show water resistance as measured by visual inspection, but in contrast to this result, the mascara composition of Example 34 showed considerable resistance to water washing.

Example 36
Sunscreen compositions were prepared using the amounts (grams) of ingredients listed in Table 10 below.

  Water resistance was determined by measuring the SPF of each sunscreen composition before and after the water wash test. Water resistance of sunscreen compositions was tested by immersing each in vitro skin section (Vitro-Skin®, IMS Inc.) to which each sunscreen composition had been applied in water for 40 minutes and then drying. did.

  The results of the water wash test are shown in Table 11 below.

  As these data show, the sunscreen of Example 35 not only shows a higher SPF than the sunscreen SPF of Comparative Example 3, but after soaking, the SPF of the sunscreen of Example 35 is increased, whereas Thus, the SPF of sunscreen of Comparative Example 3 after immersion was reduced by about 40% compared to the level before immersion.

Although the present disclosure has been described with reference to preferred embodiments, various modifications can be made and equivalents can be substituted for the elements by those skilled in the art without departing from the scope of the disclosure It is understood. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the disclosure without departing from the essential scope thereof. Accordingly, this disclosure is not limited to the specific embodiments disclosed as the best mode contemplated for carrying out this disclosure, but includes all embodiments that fall within the scope of the appended claims. Shall be.

Claims (23)

(A) Organosiloxane monomer of the general formula M _a ^Mv _{b Dc} D ^v _{d Te} T ^v _f Q _g where M = R ₁ R ₂ R ₃ SiO _1/2 ,
^{_{M v = R 4 R 5 R}} u SiO 1/2,
D = R ₆ R ₇ SiO _2/2 ,
^{_{D v = R 8 R u SiO}} 2/2,
T = R ₉ SiO _3/2 ,
T ^v = R _u SiO _3/2 and Q = SiO _4/2
Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ each independently have hydrogen, a hydroxyl group, up to 100 carbon atoms, A hydrocarbyl group which may contain at least one heteroatom; R _u is a free radical polymerizable group; subscripts a, b, c, d, e, f and g are each independently 0-10 And b + d + f is a condition of at least 1, p, q and r are integers independently selected from 0 to 100, the subscript h is 0 or 1, and ( b) Hydrophobic hybrid organosiloxane nanolatex containing a copolymer of a monomer having a group R _u of the organosiloxane monomer (a) and a free radical copolymerizable group.   The hydrophobic hybrid organosiloxane nanolatex of claim 1 in the form of a film having a contact angle of at least 50 °.   The hydrophobic hybrid organosiloxane nanolatex of claim 1 in the form of a film having a contact angle of at least 60 °.   The hydrophobic hybrid organosiloxane nanolatex of claim 1 in the form of a film having a contact angle of at least 70 °. In the organosiloxane monomer (a), each R _u is independently an ethylenically unsaturated group selected from Formulas I, II (a), II (b) and II (c);

Wherein each R ₁₀ is independently selected from a linear or branched alkyl group of up to 10 carbon atoms, which may contain at least one heteroatom; A ₁ and A ₂ are each independently free The hydrophobic hybrid organosiloxane nanolatex according to claim 1, wherein the group is capable of undergoing a radical addition reaction; and the subscripts p, q and r each independently range from 0 to 100. A ₁ and A ₂ are each independently a group of formula III;

Where R ₁₁ , R ₁₂ and R ₁₃ are each independently hydrogen or a hydrocarbyl group of up to 5 carbon atoms, Y is absent or at least one of 2 to 16 carbon atoms The hydrophobic hybrid organosiloxane nanolatex according to claim 5, which is a linking group selected from the group consisting of a divalent aliphatic, alicyclic or aromatic hydrocarbon group which may contain a hetero atom.   The monomer (a) is selected from the group consisting of vinyl functional silicone, hydroxy functional silicone acrylate, organic modified silicone (meth) acrylate, organic modified silicone acrylamide, organic modified silicone (meth) acrylamide, derivatives thereof and mixtures thereof The hydrophobic hybrid organosiloxane nanolatex according to claim 1.   The hydrophobic hybrid organosiloxane nanolatex according to claim 1, wherein the monomer (b) is selected from the group consisting of acrylic acid, methacrylic acid, esters thereof, amide derivatives thereof, and mixtures thereof.   Monomer (b) is methyl methacrylate, butyl acrylate, propyl acrylate, tert-butyl methacrylate, N, N-dimethylacrylamide, N-isopropylacrylamide, 2-ethylhexyl acrylate, cyclohexyl acrylate, vinyl acrylate, allyl acrylate, hydroxyethyl acrylate, Perfluoroethyl acrylate, isobornyl acrylate, lauryl methacrylate, lauryl arylate, cetyl methacrylate, behenyl acrylate, phenoxyethyl acrylate, tetraethylene glycol diacrylate, tripropylene glycol diacrylate, acrylamide, methacrylamide, acrylated silane, methacrylated silane, Methacryloxylsilane, 2-H Roxyethyl methacrylate, 3- [tris (trimethylsiloxy) silyl] propyl methacrylate, acrylate and methacrylate functional carbosilane, hexafunctional urethane acrylate, dipentaerythritol pentaacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, penta Erythritol triacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, butanediol diacrylate, tripropylene glycol diacrylate, trimethylolpropane trimethacrylate, oligofunctional urethane acrylate, tetraacrylate monomer, polyester acrylate oligomer, butadiene Claims selected from the group consisting of styrene, ethylstyrene, divinylbenzene, N-vinylpyrrolidone, N-vinyl lactam, vinyl halide, vinyl acetate, vinyl alcohol, vinyl ether, allyl alcohol, allyl polyether, and combinations thereof. Item 10. The hydrophobic hybrid organosiloxane nanolatex according to Item 1.   The hydrophobic hybrid organosiloxane nanolatex according to claim 1, wherein the copolymer has a particle size of 10 to 990 nm.   The hydrophobic hybrid organosiloxane nanolatex according to claim 1, wherein the copolymer has a particle size of 30 to 750 nm.   The hydrophobic hybrid organosiloxane nanolatex according to claim 1, wherein the copolymer has a particle size of 50 to 500 nm.   The hydrophobic hybrid organosiloxane nanolatex according to claim 1, wherein the content of the copolymer is 0.1 to 40% by weight of the latex.   The hydrophobic hybrid organosiloxane nanolatex according to claim 1, wherein the content of the copolymer is 0.1 to 35% by weight of the latex.   The hydrophobic hybrid organosiloxane nanolatex according to claim 7, which is a copolymer of the monomer (a) and at least two monomers (b).   A personal care composition comprising a film-forming amount of the hydrophobic hybrid organosiloxane nanolatex of claim 1.   The personal care composition of claim 16, wherein the film obtained from the hydrophobic hybrid organosiloxane nanolatex has a contact angle of at least 50 °.   17. A personal care composition according to claim 16, wherein the film obtained from the hydrophobic hybrid organosiloxane nanolatex has a contact angle of at least 60 [deg.].   The personal care composition of claim 16, wherein the film obtained from the hydrophobic hybrid organosiloxane nanolatex has a contact angle of at least 70 °.   Deodorant, Antiperspirant, Antiperspirant / Deodorant, Stick and Roll-on product, Skin lotion, Moisturizer, Cosmetic liquid, Cleansing product, Styling gel, Hair dye, Hair color product, Hair straightener, Nail polish, Nail polish・ Remover, sunscreen, anti-aging products, lipstick, lip balm, lip gloss, foundation, face powder, eyeliner, eye shadow, blusher, makeup, essence, mascara, moisturizing preparation, foundation, concealer, body and Hand preparations, skin care preparations, face and neck preparations, fragrance preparations, soft focus applications, night and day skin care preparations, tanning preparations, hand liquids, -Sonar non-woven application, baby lotion, facial cleansing product, hair cuticle coat, gel, foam bath, body wash, scrub cleaner, controlled release personal care product, hair shampoo, hair conditioner, hair spray, skin care moisturizing mist, skin wipe, For pore skin wipes, pore cleansing agents, injury relieving agents, skin release agents, skin exfoliation promoters, skin turrets and cloths, hair removal preparations, personal care lubricants, nail coloring preparations, and skin 17. A personal care composition according to claim 16 selected from the group consisting of drug delivery systems for topical application of the applied pharmaceutical composition.   21. A personal care composition according to claim 20, wherein the film obtained from the hydrophobic hybrid organosiloxane nanolatex has a contact angle of at least 50 [deg.].   21. A personal care composition according to claim 20, wherein the film obtained from the hydrophobic hybrid organosiloxane nanolatex has a contact angle of at least 60 [deg.]. 21. A personal care composition according to claim 20, wherein the film obtained from the hydrophobic hybrid organosiloxane nanolatex has a contact angle of at least 70 [deg.].